EP0275771A1 - Process for the preparation of tetrahydro-1,1,2,2-perfluoroalcanols and their esters - Google Patents
Process for the preparation of tetrahydro-1,1,2,2-perfluoroalcanols and their esters Download PDFInfo
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- EP0275771A1 EP0275771A1 EP87402923A EP87402923A EP0275771A1 EP 0275771 A1 EP0275771 A1 EP 0275771A1 EP 87402923 A EP87402923 A EP 87402923A EP 87402923 A EP87402923 A EP 87402923A EP 0275771 A1 EP0275771 A1 EP 0275771A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/34—Halogenated alcohols
- C07C31/38—Halogenated alcohols containing only fluorine as halogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/34—Halogenated alcohols
- C07C31/40—Halogenated alcohols perhalogenated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
- C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
- C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/63—Halogen-containing esters of saturated acids
Definitions
- the present invention relates to the synthesis of tetrahydro-1,1,2,2 perfluoroalkanols (R F CH2CH2OH) and their esters by oxidation of the corresponding 2-perfluoroalkylethyl iodides (R F CH2CH2I) using hydrogen peroxide.
- the perfluoroalkyl radical R F can contain from 1 to 20 carbon atoms and can be straight or branched chain.
- polyfluorinated alcohols and esters are useful intermediates for the manufacture of surfactants and hydrophobic and oleophobic products. They can in particular be easily transformed into acrylic or methacrylic esters, the polymerization of which, optionally with other monomers, provides hydrophobic and oleophobic finishing agents for textiles, leather, paper or other substrates. The mixtures of alcohols and esters can also be entirely transformed into alcohols.
- esters R F CH2CH2OCOR by reaction of an iodide R F CH2CH2I with a carboxylic acid salt RCOOH.
- the alcohols R F CH2CH2OH can also be obtained according to the process of patent FR 2 096 179 which consists in preparing the nitrates R F CH2CH2ONO2 by reaction of the iodides R F CH2CH2I with nitric acid and in hydrogenating these nitrates into alcohol.
- this process has the drawback of requiring two reaction stages, the last of which must be carried out under high hydrogen pressure.
- Patent FR 2 180 113 describes a process for manufacturing mixtures of alcohols R F CH2CH2OH and formates R F CH2CH2OCOH by reaction at high temperature of iodides R F CH2CH2I with dimethylformamide in the presence of a little water.
- good selectivity for alcohol and formate can only be obtained by using very large amounts of dimethylformamide.
- the process according to the invention which consists in oxidizing a 2-perfluoroalkylethyl iodide by means of hydrogen peroxide within a carboxylic acid or an ester of such an acid and in the presence of sulfuric acid is characterized in that, for one mole of 2-perfluoroalkylethyl iodide, 1 to 30 moles of sulfuric acid (preferably 3 to 10 moles), 1 to 50 moles of carboxylic acid or ester of such an acid (preferably 5 to 15 moles), and 3 to 20 moles of hydrogen peroxide (preferably 5 to 6 moles).
- Hydrogen peroxide is advantageously used in the form of aqueous solutions, the H2O2 concentration of which can vary from approximately 35 to 75% by weight and is preferably between 65 and 75%.
- sulfuric acid solutions containing up to 50% by weight of water.
- liquid aliphatic acids are preferably used under the operating conditions; these acids which generally contain from 1 to 8 carbon atoms can be linear or branched, saturated or not, and contain substituents such as, for example, halogen atoms. Particularly suitable are acetic acid and propionic acid.
- solid carboxylic acids such as heavy aliphatic acids or aromatic acids (for example benzoic acid and its substituted derivatives) by adding a solvent such as an alcohol (for example, methanol, ethanol, propanol) or an ester.
- a solvent such as an alcohol (for example, methanol, ethanol, propanol) or an ester.
- a carboxylic acid ester can be used.
- This ester is preferably an aliphatic alcohol ester containing 1 to 4 carbon atoms, for example ethyl acetate, butyl acetate or ethyl propionate.
- the oxidation according to the invention can be carried out at a temperature which can range from -20 to 140 ° C., but advantageously between 60 and 90 ° C.
- the method according to the invention can be carried out in different ways.
- the preferred embodiment of the invention consists in introducing hydrogen peroxide into a mixture of 2-perfluoroalkylethyl iodide, sulfuric acid and carboxylic acid or ester. This introduction is advantageously carried out with vigorous stirring with a flow rate such that the temperature of the reaction medium is itself maintained between 60 and 90 ° C.
- the reaction is generally very rapid and takes place with a release of iodine and / or iodic acid which can be easily separated from the reaction mixture by simple filtration. Most of the iodine can thus be recovered in the form of elementary iodine by treatment of iodic acid with a conventional reducing agent such as sodium sulfite.
- the fluorinated products can be isolated according to the usual methods, for example by decantation and washing of the organic phase with water. Finally, a product is obtained which consists mainly of the 2-perfluoroalkyl ethyl ester (R F C2H4OCOR) which can be saponified to obtain the alcohol R F CH2CH2OH or transform into another ester, in particular into acrylate or methacrylate.
- R F C2H4OCOR 2-perfluoroalkyl ethyl ester
- reaction mixture is then filtered to separate the iodine and the iodic acid formed, then the filtrate is decanted and the organic phase is washed three times with 50 ml of water at 25 ° C.
- the distribution of fluorinated compounds in the organic phase thus obtained is as follows: 97.8% of R F C2H4OCOC2H5 2% of R F C2H4OH 0.2% of R F C2H4I unprocessed.
- Example 2 is repeated, hand replacing the propionic acid with 88 g of ethyl acetate. 38 g of organic phase are then obtained, the fluorinated compounds of which are distributed as follows: 79.3% of C6F13C2H4OCOCH3 18.2% of C6F13C2H4OH 2.5% of unprocessed C6F13C2H4I.
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Abstract
Description
La présente invention concerne la synthèse des tétrahydro-1,1,2,2 perfluoroalcanols (RFCH₂CH₂OH) et de leurs esters par oxydation des iodures de perfluoroalkyl-2 éthyle correspondants (RFCH₂CH₂I) au moyen du peroxyde d'hydrogène. Le radical perfluoroalkyle RF peut contenir de 1 à 20 atomes de carbone et être à chaîne linéaire ou ramifiée.The present invention relates to the synthesis of tetrahydro-1,1,2,2 perfluoroalkanols (R F CH₂CH₂OH) and their esters by oxidation of the corresponding 2-perfluoroalkylethyl iodides (R F CH₂CH₂I) using hydrogen peroxide. The perfluoroalkyl radical R F can contain from 1 to 20 carbon atoms and can be straight or branched chain.
Ces alcools et esters polyfluorés sont des intermédiaires intéressants pour la fabrication d'agents tensioactifs et de produits hydrophobes et oléophobes. Ils peuvent en particulier être facilement transformés en esters acryliques ou méthacryliques dont la polymérisation, éventuellement avec d'autres monomères, fournit des agents d'apprêt hydrophobe et oléophobe pour les matières textiles, le cuir, le papier ou d'autres substrats. Les mélanges d'alcools et d'esters peuvent aussi être transformés entièrement en alcools.These polyfluorinated alcohols and esters are useful intermediates for the manufacture of surfactants and hydrophobic and oleophobic products. They can in particular be easily transformed into acrylic or methacrylic esters, the polymerization of which, optionally with other monomers, provides hydrophobic and oleophobic finishing agents for textiles, leather, paper or other substrates. The mixtures of alcohols and esters can also be entirely transformed into alcohols.
Plusieurs procédés de préparation de ces alcools et esters polyfluorés sont déjà connus. Le procédé décrit dans le brevet FR 1 380 579 qui consiste à faire réagir un iodure RFCH₂CH₂I avec de l'oléum puis à hydrolyser le sulfate formé, présente l'inconvénient de fournir des quantités importantes de diesters sulfuriques qui sont difficilement hydrolysables.Several processes for the preparation of these polyfluorinated alcohols and esters are already known. The process described in patent FR 1 380 579 which consists in reacting an iodide R F CH₂CH₂I with oleum and then in hydrolyzing the sulphate formed, has the drawback of providing large quantities of sulfuric diesters which are difficult to hydrolyze.
Selon un procédé décrit dans le brevet US 3 239 557 il est possible d'obtenir les esters RFCH₂CH₂OCOR par réaction d'un iodure RFCH₂CH₂I avec un sel d'acide carboxylique RCOOH. Les rendements ne sont cependant pas trés bons car il se forme des quantités plus ou moins importantes d'oléfine RFCH=CH₂.According to a process described in US Pat. No. 3,239,557, it is possible to obtain the esters R F CH₂CH₂OCOR by reaction of an iodide R F CH₂CH₂I with a carboxylic acid salt RCOOH. The yields are however not very good because more or less significant quantities of olefin R F CH = CH₂ are formed.
Les alcools RFCH₂CH₂OH peuvent aussi être obtenus selon le procédé du brevet FR 2 096 179 qui consiste à préparer les nitrates RFCH₂CH₂ONO₂ par réaction des iodures RFCH₂CH₂I avec l'acide nitrique et à hydrogéner ces nitrates en alcool. Ce procédé présente toutefois l'inconvénient de nécessiter deux étapes réactionnelles dont la dernière doit être réalisée sous une pression élevée d'hydrogène.The alcohols R F CH₂CH₂OH can also be obtained according to the process of patent FR 2 096 179 which consists in preparing the nitrates R F CH₂CH₂ONO₂ by reaction of the iodides R F CH₂CH₂I with nitric acid and in hydrogenating these nitrates into alcohol. However, this process has the drawback of requiring two reaction stages, the last of which must be carried out under high hydrogen pressure.
Le brevet FR 2 180 113 décrit un procédé de fabrication de mélanges d'alcools RFCH₂CH₂OH et de formiates RFCH₂CH₂OCOH par réaction à haute température des iodures RFCH₂CH₂I avec le diméthylformamide en présence d'un peu d'eau. Ce procédé présente l'inconvénient d'exiger des conditions de réaction trés sévères et de fournir comme sous-produit l'oléfine RFCH=CH₂, ce qui diminue d'autant le rendement. Une bonne sélectivité en alcool et formiate ne peut en outre être obtenue qu'en utilisant des quantités trés importantes de diméthylformamide.Patent FR 2 180 113 describes a process for manufacturing mixtures of alcohols R F CH₂CH₂OH and formates R F CH₂CH₂OCOH by reaction at high temperature of iodides R F CH₂CH₂I with dimethylformamide in the presence of a little water. This process has the drawback of requiring very severe reaction conditions and of supplying the olefin R F CH = CH₂ as a by-product, which consequently reduces the yield. In addition, good selectivity for alcohol and formate can only be obtained by using very large amounts of dimethylformamide.
Plus récemment, ou a proposé dans les brevets EP 0024224 et DE 3 035 641 de préparer ces alcools et esters polyfluorés en faisant réagir l'iodure RFCH₂CH₂I avec un peracide RCO₃H préalablement formé par l'addition de peroxyde d'hydrogène à un acide carboxylique RCO₂H en présence ou non d'une faible quantité d'acide sulfurique. Cependant, dans les conditions opératoires décrites, ce procédé conduit à une sous-production d'oléfine RFCH=CH₂ en quantité non négligeable et/ou à un faible taux de conversion de l'iodure RFCH₂CH₂I.More recently, or has proposed in patents EP 0024224 and DE 3,035,641 to prepare these polyfluorinated alcohols and esters by reacting the iodide R F CH₂CH₂I with a peracid RCO₃H previously formed by the addition of hydrogen peroxide to an acid carboxylic RCO₂H in the presence or not of a small amount of sulfuric acid. However, under the operating conditions described, this process leads to an under-production of olefin R F CH = CH₂ in a non-negligible amount and / or to a low conversion rate of iodide R F CH₂CH₂I.
Il a maintenant été trouvé un procédé permettant de pallier ces inconvénients, c'est-à-dire d'éviter une sous-production d'oléfine RFCH=CH₂ et d'obtenir néanmoins un taux de conversion trés élevé.A process has now been found which makes it possible to overcome these drawbacks, that is to say to avoid an under-production of olefin R F CH = CH₂ and nevertheless obtain a very high conversion rate.
Le procédé selon l'invention qui consiste à oxyder un iodure de perfluoroalkyl-2 éthyle au moyen du peroxyde d'hydrogène au sein d'un acide carboxylique ou d'un ester d'un tel acide et en présence d'acide sulfurique est caractérisé en ce que, pour une mole d'iodure de perfluoroalkyl-2 éthyle, on met en oeuvre de 1 à 30 moles d'acide sulfurique (de préférence,de 3 à 10 moles), de 1 à 50 moles d'acide carboxylique ou d'ester d'un tel acide (de préférence, de 5 à 15 moles), et de 3 à 20 moles de peroxyde d'hydrogène (de préférence, 5 à 6 moles).The process according to the invention which consists in oxidizing a 2-perfluoroalkylethyl iodide by means of hydrogen peroxide within a carboxylic acid or an ester of such an acid and in the presence of sulfuric acid is characterized in that, for one mole of 2-perfluoroalkylethyl iodide, 1 to 30 moles of sulfuric acid (preferably 3 to 10 moles), 1 to 50 moles of carboxylic acid or ester of such an acid (preferably 5 to 15 moles), and 3 to 20 moles of hydrogen peroxide (preferably 5 to 6 moles).
Le peroxyde d'hydrogène est avantageusement utilisé sous forme de solutions aqueuses dont la concentration en H₂O₂ peut varier d'environ 35 à 75 % en poids et est de préférence comprise entre 65 et 75 %.Hydrogen peroxide is advantageously used in the form of aqueous solutions, the H₂O₂ concentration of which can vary from approximately 35 to 75% by weight and is preferably between 65 and 75%.
Bien qu'on préfère utiliser l'acide sulfurique pur ou trés concentré (80 % en poids et plus), on peut également employer des solutions d'acide sulfurique contenant jusqu'à 50 % en poids d'eau.Although it is preferred to use pure or very concentrated sulfuric acid (80% by weight and more), it is also possible to use sulfuric acid solutions containing up to 50% by weight of water.
Comme acides carboxyliques, on utilise de préférence les acides aliphatiques liquides dans les conditions opératoires ; ces acides qui contiennent généralement de 1 à 8 atomes de carbone peuvent être linéaires ou ramifiés, saturés ou non, et contenir des substituants tels que, par exemple, des atomes d'halogène. Conviennent particulièrement bien l'acide acétique et l'acide propionique.As carboxylic acids, liquid aliphatic acids are preferably used under the operating conditions; these acids which generally contain from 1 to 8 carbon atoms can be linear or branched, saturated or not, and contain substituents such as, for example, halogen atoms. Particularly suitable are acetic acid and propionic acid.
On peut également utiliser des acides carboxyliques solides tels que les acides aliphatiques lourds ou les acides aromatiques (par exemple l'acide benzoïque et ses dérivés substitués) en ajoutant un solvant tel qu'un alcool (par exemple, méthanol, éthanol, propanol) ou un ester.It is also possible to use solid carboxylic acids such as heavy aliphatic acids or aromatic acids (for example benzoic acid and its substituted derivatives) by adding a solvent such as an alcohol (for example, methanol, ethanol, propanol) or an ester.
Comme indiqué précédemment, on peut utiliser un ester d'acide carboxylique. Cet ester est de préférence un ester d'alcool aliphatique contenant 1 à 4 atomes de carbone, par exemple l'acétate d'éthyle, l'acétate de butyle ou le propionate d'éthyle.As indicated previously, a carboxylic acid ester can be used. This ester is preferably an aliphatic alcohol ester containing 1 to 4 carbon atoms, for example ethyl acetate, butyl acetate or ethyl propionate.
L'oxydation selon l'invention peut être effectuée à une température pouvant aller de -20 à 140°C, mais avantageusement comprise entre 60 et 90°C.The oxidation according to the invention can be carried out at a temperature which can range from -20 to 140 ° C., but advantageously between 60 and 90 ° C.
Le procédé selon l'invention peut être réalisé de différentes façons. On peut par exemple opérer comme dans les brevets EP 0024224 et DE 3 035 641 en ajoutant au iodure de perfluoroalkyl-2 éthyle un mélange de peroxyde d'hydrogène, d'acide sulfurique et d'acide carboxylique ou d'ester dans les proportions requises. Il est également possible d'opérer de façon inverse en introduisant l'iodure dans un tel mélange.The method according to the invention can be carried out in different ways. One can for example operate as in patents EP 0024224 and DE 3,035,641 by adding to the perfluoroalkyl-2 ethyl iodide a mixture of hydrogen peroxide, sulfuric acid and carboxylic acid or ester in the required proportions . It is also possible to operate in reverse by introducing iodide into such a mixture.
Cependant, le mode de réalisation préféré de l'invention consiste à introduire le peroxyde d'hydrogène dans un mélange de l'iodure de perfluoroalkyl-2 éthyle, d'acide sulfurique et de l'acide ou ester carboxylique. Cette introduction est avantageusement effectuée sous agitation énergique avec un débit tel que la température du milieu réactionnel se maintienne d'elle-même entre 60 et 90°C.However, the preferred embodiment of the invention consists in introducing hydrogen peroxide into a mixture of 2-perfluoroalkylethyl iodide, sulfuric acid and carboxylic acid or ester. This introduction is advantageously carried out with vigorous stirring with a flow rate such that the temperature of the reaction medium is itself maintained between 60 and 90 ° C.
La réaction est en général trés rapide et se fait avec une libération d'iode et/ou d'acide iodique qu'on peut séparer facilement du mélange réactionnel par simple filtration. La majeure partie de l'iode peut ainsi être récupérée sous forme d'iode élémentaire par traitement de l'acide iodique avec un réducteur classique tel que le sulfite de sodium.The reaction is generally very rapid and takes place with a release of iodine and / or iodic acid which can be easily separated from the reaction mixture by simple filtration. Most of the iodine can thus be recovered in the form of elementary iodine by treatment of iodic acid with a conventional reducing agent such as sodium sulfite.
Les produits fluorés peuvent êtres isolés suivant les méthodes habituelles, par exemple par décantation et lavage de la phase organique à l'eau. On obtient finalement un produit constitué majoritairement par l'ester de perfluoroalkyl-2 éthyle (RFC₂H₄OCOR) qu'on peut saponifier pour obtenir l'alcool RFCH₂CH₂OH ou transformer en un autre ester, notamment en acrylate ou méthacrylate.The fluorinated products can be isolated according to the usual methods, for example by decantation and washing of the organic phase with water. Finally, a product is obtained which consists mainly of the 2-perfluoroalkyl ethyl ester (R F C₂H₄OCOR) which can be saponified to obtain the alcohol R F CH₂CH₂OH or transform into another ester, in particular into acrylate or methacrylate.
Comme cela est déjà signalé dans le brevet DE 3.035.641 précité, le travail avec les peracides et le peroxyde d'hydrogène comporte d'importants risques d'inflammation et d'explosion. Il conviendra donc, lors de la mise en oeuvre du procédé selon l'invention, de prendre à cet égard toutes les mesures de précaution usuelles.As already mentioned in the aforementioned patent DE 3,035,641, working with peracids and hydrogen peroxide involves significant risks of ignition and explosion. It will therefore be necessary, when implementing the method according to the invention, to take in this respect all the usual precautionary measures.
Les exemples suivants dans lesquels les pourcentages s'entendent en poids, illustrent l'invention sans la limiter.The following examples, in which the percentages are by weight, illustrate the invention without limiting it.
Dans un réacteur en verre de 250 ml, muni d'un agitateur énergique, d'un réfrigérant à reflux et d'une ampoule de coulée, on charge 47,4 g (0,1 mole) d'iodure de perfluorohexyl-2 éthyle, 60 g d'acide acétique et 28 ml d'acide sulfurique à 98 %, puis on ajoute goutte à goutte en 50 minutes 24,7 g d'une solution à 70 % de peroxyde d'hydrogène (soit 0,5 mole de H₂O₂). La température s'élève d'elle-même à 75-80°C et est maintenue à cette valeur pendant encore 30 à 45 minutes aprés la fin de l'addition.47.4 g (0.1 mol) of 2-perfluorohexylethyl iodide are charged into a 250 ml glass reactor, equipped with a vigorous stirrer, a reflux condenser and a dropping funnel , 60 g of acetic acid and 28 ml of 98% sulfuric acid, then 24.7 g of a 70% solution of hydrogen peroxide (i.e. 0.5 mole of H₂O₂). The temperature rises by itself to 75-80 ° C and is maintained at this value for another 30 to 45 minutes after the end of the addition.
Le mélange réactionnel est ensuite filtré pour séparer l'iode et l'acide iodique formés, puis on décante le filtrat et on lave la phase organique trois fois avec 50 ml d'eau à 25°C.The reaction mixture is then filtered to separate the iodine and the iodic acid formed, then the filtrate is decanted and the organic phase is washed three times with 50 ml of water at 25 ° C.
On obtient ainsi 38 g de phase organique dont la répartition des composés fluorés, déterminée par chromatographie, est la suivante :
95 % de C₆F₁₃C₂H₄OCOCH₃
3,1 % de C₆F₁₃C₂H₄OH
1,5 % de (C₆F₁₃C₂H₄O)₂SO₂
0,4 % de C₆F₁₃C₂H₄I non transformé.38 g of organic phase are thus obtained, the distribution of the fluorinated compounds, determined by chromatography, is as follows:
95% of C₆F₁₃C₂H₄OCOCH₃
3.1% of C₆F₁₃C₂H₄OH
1.5% of (C₆F₁₃C₂H₄O) ₂SO₂
0.4% of unprocessed C₆F₁₃C₂H₄I.
Dans un réacteur identique à celui de l'exemple 1, on charge 47,4 g d'iodure de perfluorohexyl-2 éthyle, 30 ml d'acide sulfurique à 98 % et 74 g d'acide propionique, puis on ajoute goutte à goutte en 45 minutes 26,9 g d'une solution à 70 % de peroxyde d'hydrogène et on maintient ensuite pendant encore 30 minutes à 75-80°C sous agitation.In a reactor identical to that of Example 1, 47.4 g of 2-perfluorohexyl ethyl iodide, 30 ml of 98% sulfuric acid and 74 g of propionic acid are charged, then added dropwise in 45 minutes 26.9 g of a 70% solution of hydrogen peroxide and then maintained for another 30 minutes at 75-80 ° C with stirring.
Aprés filtration, décantation du filtrat et lavage au sulfite de sodium et à l'eau, on récupère 40 g de phase organique dont la répartition des composés fluorés est la suivante :
98,4 % de C₆F₁₃C₂H₄OCOC₂H₅
1,4 % de C₆F₁₃C₂H₄OH
0,2 % de C₆F₁₃C₂H₄I non transformé.After filtration, decantation of the filtrate and washing with sodium sulfite and with water, 40 g of organic phase are recovered, the distribution of the fluorinated compounds is as follows:
98.4% of C₆F₁₃C₂H₄OCOC₂H₅
1.4% of C₆F₁₃C₂H₄OH
0.2% of unprocessed C₆F₁₃C₂H₄I.
En opérant comme à l'exemple 2 à partir de 37,4 g d'iodure de perfluorobutyl-2 éthyle, on obtient 28 g de phase organique dont la répartition des composés fluorés est la suivante :
97 % de C₄F₉C₂H₄OCOC₂H₅
1,5 % de C₄F₉C₂H₄OH
1,5 % de C₄F₉C₂H₄I non transformé.By operating as in Example 2 from 37.4 g of 2-perfluorobutyl ethyl iodide, 28 g of organic phase are obtained, the distribution of the fluorinated compounds being as follows:
97% of C₄F₉C₂H₄OCOC₂H₅
1.5% of C₄F₉C₂H₄OH
1.5% of unprocessed C₄F₉C₂H₄I.
On opère comme à l'exemple 2, mais en remplaçant l'iodure de perfluorohexyl-2 éthyle par 53,8 g d'un mélange d'iodures RFC₂H₄I ayant la composition pondérale suivante :
La répartition des composés fluorés dans la phase organique ainsi obtenue (40 g) est la suivante :
97,8 % de RFC₂H₄OCOC₂H₅
2 % de RFC₂H₄OH
0,2 % de RFC₂H₄I non transformés.The distribution of fluorinated compounds in the organic phase thus obtained (40 g) is as follows:
97.8% of R F C₂H₄OCOC₂H₅
2% of R F C₂H₄OH
0.2% of R F C₂H₄I unprocessed.
En opérant comme à l'exemple 2 à partir de 27,4 g de iodure de pentafluoro-3,3,4,4,4 butyle, on obtient 20 g de phase organique dont les composés fluorés se répartissent comme suit :
96,5 % de C₂F₅C₂H₄OCOC₂H₅
1,5 % de C₂F₅C₂H₄OH
2 % de C₂F₅C₂H₄I non transformé.By operating as in Example 2 from 27.4 g of pentafluoro-3,3,4,4,4 butyl iodide, 20 g of organic phase are obtained, the fluorinated compounds of which are distributed as follows:
96.5% of C₂F₅C₂H₄OCOC₂H₅
1.5% of C₂F₅C₂H₄OH
2% of unprocessed C₂F₅C₂H₄I.
Dans un réacteur identique à celui de l'exemple 1, on charge 47,4 g d'iodure de perfluorohexyl-2 éthyle, 30 ml d'acide sulfurique à 98 % et 163 g d'acide trichloroacétique. On ajoute ensuite sous agitation 26,9 g d'une solution à 70 % de peroxyde d'hydrogène à un débit tel que la température se maintienne à 70-80°C. Quand l'addition du peroxyde d'hydrogène est terminée, on laisse sous agitation pendant encore 30 minutes.47.4 g of 2-ethyl perfluorohexyl iodide, 30 ml of 98% sulfuric acid and 163 g of trichloroacetic acid are charged into a reactor identical to that of Example 1. Then added with stirring 26.9 g of a 70% solution of hydrogen peroxide at a rate such that the temperature is maintained at 70-80 ° C. When the addition of hydrogen peroxide is complete, the mixture is left stirring for a further 30 minutes.
Aprés refroidissement à 20°C, on ajoute 100 ml d'eau. Par filtration, on récupère 12,3 g d'iode brut. Aprés décantation du filtrat et lavage de la phase organique à l'eau, on obtient 53 g d'un produit dont la répartition des composés fluorés est la suivante :
90,6 % de C₆F₁₃C₂H₄OCOCCl₃
1,1 % de C₆F₁₃C₂H₄OH
5,6 % de (C₆F₁₃C₂H₄O)₂SO₂
2,7 % de C₆F₁₃C₂H₄I non transformé.After cooling to 20 ° C, 100 ml of water are added. By filtration, 12.3 g of crude iodine are recovered. After decanting the filtrate and washing the organic phase with water, 53 g of a product are obtained, the distribution of the fluorinated compounds is as follows:
90.6% of C₆F₁₃C₂H₄OCOCCl₃
1.1% of C₆F₁₃C₂H₄OH
5.6% of (C₆F₁₃C₂H₄O) ₂SO₂
2.7% of unprocessed C₆F₁₃C₂H₄I.
On opère comme à l'exemple 2, main en remplaçant les 74 g d'acide propionique par 144 g d'acide octanoïque. On obtient ainsi 56 g de phase organique dont les composés fluorés se répartissent comme suit :
98 % de C₆F₁₃C₂H₄OCOC₇H₁₅
0,8 % de C₆F₁₃C₂H₄OH
1,2 % de C₆F₁₃C₂H₄I non transformé.The procedure is as in Example 2, hand, replacing the 74 g of propionic acid with 144 g of octanoic acid. 56 g of organic phase are thus obtained, the fluorinated compounds of which are distributed as follows:
98% of C₆F₁₃C₂H₄OCOC₇H₁₅
0.8% of C₆F₁₃C₂H₄OH
1.2% of unprocessed C₁₃F₂C₂H₄I.
On répète l'exemple 2, main en remplaçant l'acide propionique par 88 g d'acétate d'éthyle. On obtient alors 38 g de phase organique dont les composés fluorés se répartissent comme suit :
79,3 % de C₆F₁₃C₂H₄OCOCH₃
18,2 % de C₆F₁₃C₂H₄OH
2,5 % de C₆F₁₃C₂H₄I non transformé.Example 2 is repeated, hand replacing the propionic acid with 88 g of ethyl acetate. 38 g of organic phase are then obtained, the fluorinated compounds of which are distributed as follows:
79.3% of C₆F₁₃C₂H₄OCOCH₃
18.2% of C₆F₁₃C₂H₄OH
2.5% of unprocessed C₆F₁₃C₂H₄I.
Claims (7)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT87402923T ATE45346T1 (en) | 1986-12-22 | 1987-12-18 | PRODUCTION PROCESSES OF TETRAHYDRO-1,1,2,2PERFLUOROALKANOLS AND THEIR ESTERS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8617983 | 1986-12-22 | ||
FR8617983 | 1986-12-22 |
Publications (2)
Publication Number | Publication Date |
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EP0275771A1 true EP0275771A1 (en) | 1988-07-27 |
EP0275771B1 EP0275771B1 (en) | 1989-08-09 |
Family
ID=9342164
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87402923A Expired EP0275771B1 (en) | 1986-12-22 | 1987-12-18 | Process for the preparation of tetrahydro-1,1,2,2-perfluoroalcanols and their esters |
Country Status (12)
Country | Link |
---|---|
US (1) | US4791223A (en) |
EP (1) | EP0275771B1 (en) |
JP (1) | JPS63166840A (en) |
KR (1) | KR910000250B1 (en) |
AT (1) | ATE45346T1 (en) |
AU (1) | AU599734B2 (en) |
CA (1) | CA1265154A (en) |
DE (1) | DE3760417D1 (en) |
DK (1) | DK672687A (en) |
ES (1) | ES2010714B3 (en) |
FI (1) | FI875684A (en) |
NO (1) | NO165188C (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0526976A1 (en) * | 1991-07-10 | 1993-02-10 | Minnesota Mining And Manufacturing Company | Perfluoroalkyl halides and derivatives |
US5852148A (en) * | 1991-07-10 | 1998-12-22 | Minnesota Mining & Manufacturing Company | Perfluoroalkyl halides and derivatives |
US6048952A (en) * | 1991-07-10 | 2000-04-11 | 3M Innovative Properties Company | Perfluoroalkyl halides and derivatives |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NO166122C (en) * | 1986-12-22 | 1991-06-05 | Atochem | PROCEDURE FOR THE PREPARATION OF A MIXTURE OF 1,1,2,2-TETRAHYDROPERFLUORAL CHANOLS AND THEIR ESTERS. |
JP4525884B2 (en) * | 1999-05-12 | 2010-08-18 | ダイキン工業株式会社 | Catalyst for producing fluorine-containing alcohol compound and method for producing fluorine-containing alcohol compound |
DE102004006103A1 (en) * | 2004-02-06 | 2005-10-20 | Voith Fabrics Patent Gmbh | Modular paper machine clothing |
US20070244338A1 (en) * | 2004-04-26 | 2007-10-18 | Yoshio Funakoshi | Method for Producing Fluorine-Containing Acrylic Ester |
WO2005102982A1 (en) * | 2004-04-26 | 2005-11-03 | Daikin Industries, Ltd. | Process for producing fluorinated (meth)acrylic ester |
JPWO2005102984A1 (en) * | 2004-04-26 | 2008-03-13 | ダイキン工業株式会社 | Method for producing fluorine-containing acrylic ester |
US8212064B2 (en) * | 2008-05-14 | 2012-07-03 | E.I. Du Pont De Nemours And Company | Ethylene tetrafluoroethylene intermediates |
US8318877B2 (en) * | 2008-05-20 | 2012-11-27 | E.I. Du Pont De Nemours And Company | Ethylene tetrafluoroethylene (meth)acrylate copolymers |
EP3933963A1 (en) | 2020-07-01 | 2022-01-05 | VARTA Microbattery GmbH | Method and apparatus for manufacturing electrochemical cells and electrode for an electrochemical cell |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3239557A (en) * | 1962-01-18 | 1966-03-08 | Du Pont | Process for converting halides to esters |
EP0024224A1 (en) * | 1979-08-08 | 1981-02-25 | P C U K Produits Chimiques Ugine Kuhlmann | Process for the synthesis of 1,1,2,2-tetrahydroperfluoro alcohols and their esters |
DE3035641A1 (en) * | 1980-09-20 | 1982-05-06 | Hoechst Ag, 6000 Frankfurt | Per:fluoro-alkyl-alkanol textile finish intermediate prepn. - by reacting per:fluoro-alkyl iodo-alkane with peroxido-carboxylic acid opt. using phase transfer catalyst |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1023768A (en) * | 1972-12-21 | 1978-01-03 | Horst Jager | Polyfluoroalkyl iodides, process for their manufacture, and their use |
JPS59141538A (en) * | 1983-02-01 | 1984-08-14 | Agency Of Ind Science & Technol | Production of halogenated propionic acid ester |
NO166122C (en) * | 1986-12-22 | 1991-06-05 | Atochem | PROCEDURE FOR THE PREPARATION OF A MIXTURE OF 1,1,2,2-TETRAHYDROPERFLUORAL CHANOLS AND THEIR ESTERS. |
-
1987
- 1987-11-26 NO NO874942A patent/NO165188C/en unknown
- 1987-12-04 US US07/128,825 patent/US4791223A/en not_active Expired - Fee Related
- 1987-12-18 AT AT87402923T patent/ATE45346T1/en not_active IP Right Cessation
- 1987-12-18 DE DE8787402923T patent/DE3760417D1/en not_active Expired
- 1987-12-18 EP EP87402923A patent/EP0275771B1/en not_active Expired
- 1987-12-18 ES ES87402923T patent/ES2010714B3/en not_active Expired
- 1987-12-21 DK DK672687A patent/DK672687A/en not_active Application Discontinuation
- 1987-12-21 AU AU82874/87A patent/AU599734B2/en not_active Ceased
- 1987-12-21 CA CA000555009A patent/CA1265154A/en not_active Expired - Lifetime
- 1987-12-22 FI FI875684A patent/FI875684A/en not_active Application Discontinuation
- 1987-12-22 KR KR1019870014098A patent/KR910000250B1/en not_active IP Right Cessation
- 1987-12-22 JP JP62325105A patent/JPS63166840A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3239557A (en) * | 1962-01-18 | 1966-03-08 | Du Pont | Process for converting halides to esters |
EP0024224A1 (en) * | 1979-08-08 | 1981-02-25 | P C U K Produits Chimiques Ugine Kuhlmann | Process for the synthesis of 1,1,2,2-tetrahydroperfluoro alcohols and their esters |
DE3035641A1 (en) * | 1980-09-20 | 1982-05-06 | Hoechst Ag, 6000 Frankfurt | Per:fluoro-alkyl-alkanol textile finish intermediate prepn. - by reacting per:fluoro-alkyl iodo-alkane with peroxido-carboxylic acid opt. using phase transfer catalyst |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0526976A1 (en) * | 1991-07-10 | 1993-02-10 | Minnesota Mining And Manufacturing Company | Perfluoroalkyl halides and derivatives |
US5852148A (en) * | 1991-07-10 | 1998-12-22 | Minnesota Mining & Manufacturing Company | Perfluoroalkyl halides and derivatives |
US6048952A (en) * | 1991-07-10 | 2000-04-11 | 3M Innovative Properties Company | Perfluoroalkyl halides and derivatives |
US6365769B1 (en) | 1991-07-10 | 2002-04-02 | 3M Innovative Properties Company | Perfluoroalkyl halides and derivatives |
Also Published As
Publication number | Publication date |
---|---|
AU8287487A (en) | 1988-06-23 |
FI875684A0 (en) | 1987-12-22 |
ATE45346T1 (en) | 1989-08-15 |
NO165188C (en) | 1991-01-09 |
EP0275771B1 (en) | 1989-08-09 |
JPH0416451B2 (en) | 1992-03-24 |
KR910000250B1 (en) | 1991-01-23 |
DK672687D0 (en) | 1987-12-21 |
FI875684A (en) | 1988-06-23 |
DE3760417D1 (en) | 1989-09-14 |
NO874942L (en) | 1988-06-23 |
NO874942D0 (en) | 1987-11-26 |
JPS63166840A (en) | 1988-07-11 |
KR880007415A (en) | 1988-08-27 |
NO165188B (en) | 1990-10-01 |
AU599734B2 (en) | 1990-07-26 |
DK672687A (en) | 1988-06-23 |
ES2010714B3 (en) | 1989-12-01 |
CA1265154A (en) | 1990-01-30 |
US4791223A (en) | 1988-12-13 |
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